Flexible hydraulic compositions

ABSTRACT

A composition for making flexible articles includes a hydraulic component of at least 50 weight % fly ash, a water-soluble, film-forming polymer and water. Articles are made from this composition by making a slurry of the components, forming the article and allowing it to set.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of copending U.S. Provisional Ser.No. 60/610,389, filed Sep. 16, 2004, and is related to copending U.S.Ser. No. 11/xxx,xxx, (Attorney Docket No. 2033.72409), entitled,“Flexible and Rollable Cementitious Membrane and Method of ManufacturingIt,” filed concurrently herewith, both of which are herein incorporatedby reference.

FIELD OF THE INVENTION

This invention relates to flexible hydraulic compositions. Morespecifically, this invention relates to articles made from a fly ashcomposition that can be shaped, carved and deformed, and a method tomake them.

BACKGROUND OF THE INVENTION

A large variety of hydraulic components are available and are selecteddepending on the end use of the article under construction. Outdoorstatuary, architectural moldings, mortars, grouts, tiles and the likeare often made of concrete because it withstands water and weather.Gypsum is generally reserved for indoor use, such as plaster or drywall.Both of these materials form a settable slurry when added to water thatcan be used in a variety of ways. The slurry can be applied with atrowel for patching. It can be molded to form statuary. Either materialcan be used in mortars and grouts to set tiles or bricks in place.

However, concrete and gypsum both harden to be very rigid, brittlematerials. Once set, it is not practical to change their shape. Forexample, when used as a grout for ceramic tile, if there is a shift inthe underlayment, the grout usually cracks because it cannot deform tomove with the shift. When subjected to a sudden impact, concrete andgypsum often break because they cannot absorb the force by deformation.

Another disadvantage of concrete is the length of the time needed tocure the material. Concrete cannot hold its own weight for hours, anddoes not fully cure for a week or more. When making molded articles, themolds cannot be turned around and reused until the following day. If theconcrete is used to make something that must bear the weight of otherarticles, such as the basement floor in a new house, the floor cannot beused for several days until the concrete is more fully cured.

Gypsum has a considerably shorter setting time, but has its owndisadvantage in the amount of dust generated when, for example, jointcompound is finished. To smooth the surface of a joint and feather theedges so that they blend with the adjoining dry wall, joints are sanded,creating quantities of very fine dust that can be carried greatdistances before settling out. In addition to leaving dust some distancefrom the site being patched, this fine dust becomes a nuisance to thosewho breathe it.

U.S. Pat. No. 6,455,615 to Yu discloses a flexible polymer modifiedcement that can be used alone or on a substrate. It is disclosed for usein concealed areas of construction engineering, water conservancyprojects and municipal works. A hydraulic cement, a polymer dispersionand water are calendared to form sheets, then dried until thecomposition is firm. The hydraulic component optionally includes from20% to about 50% other hydraulic components, including fly ash, silicafume, metakaolin and slag.

SUMMARY OF THE INVENTION

A composition for the manufacture of articles includes a hydrauliccomponent having at least 50% hydraulic fly ash; a water-soluble,film-forming polymer and water. This composition sets rapidly, forming aflexible, deformable solid that has many uses. Despite the relativelylow amount of polymer, the resulting composition has properties moresimilar to a plastic than a hydraulic component. Optionally, thecomposition also includes one or more additives, including dispersants,surfactants, water reducing agents, foaming agents, defoamers,colorants, shrinkage reducing agents, reinforcing fibers and fillers.

Because of the setting properties of this composition, it is useful in anumber of applications for which concrete or gypsum are traditionallyused. This flexible hydraulic composition could be used, for example, tomake quick-setting, flexible tiles. Such tiles could be used to build acurved wall. It could be used for a floating floor, such as a dancefloor, that has some “give” to it and is easier on the feet of thedancers.

Flexible compositions of this type are also useful because they are lessbrittle, and can be treated with tools to provide greater detail orbetter fit than concrete or gypsum articles. Articles made from thiscomposition can be shaped with conventional tools to add architecturaldetails, artistic details or to improve the fit. When shaped or sanded,this material does not produce the type of fines associated with gypsum,but instead produces particles that are heavy enough to cleanly drop outof the air. The reduced brittleness of the material also producesarticles that are less likely to break or crack as a result of anexternal impact.

In addition, articles made from this composition are substantiallyimpermeable to water. It can be used as a water-proofing material.Grouts and mortars made from this composition do not require sealing toprevent absorption of liquids that might stain or discolor them.

Further, articles can be molded, including injection molding, to make awide variety of articles. Once made, these articles are less breakablebecause forces can be absorbed by deformation of the article, ratherthan breakage of the article. Statuary is less brittle. Architecturalmoldings and details do not break. There are many uses for a strong,settable material that is not brittle.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a flexed panel made with the composition of the presentinvention;

FIG. 2 shows a patty cast from of the composition of Mix 1 of Example 1;

FIG. 3 shows a patty cast from the composition of Mix 3 of Example 1having no fly ash present;

FIG. 4 shows a patty cast from Mix 2 of Example 1 having 50% fly ash;

FIG. 5 shows a patty cast from the composition of Mix 4 of Example 4;

FIG. 6 shows a patty cast from the composition of Mix 5 of Example 4;and

FIG. 7 shows a patty cast from the composition of Mix 6 of Example 4.

DETAILED DESCRIPTION OF THE INVENTION

The composition of the present invention includes a hydraulic component,a polymer and water. Unless otherwise noted, amounts or concentrationsreported herein describing the compositions are on a weight basis.

Any hydraulic components that include at least 50% fly ash are useful inthe instant composition. Class C hydraulic fly ash, or its equivalent,is the most preferred hydraulic component. This type of fly ash is ahigh lime content fly ash that is obtained from the processing ofcertain coals. ASTM designation C-618, herein incorporated by reference,describes the characteristics of Class C fly ash (Bayou Ash Inc., BigCajun,II, La.). When mixed with water, the fly ash sets similarly to acement or gypsum. Use of other hydraulic components in combination withfly ash are contemplated, including cements, including high aluminacements, calcium sulfates, including calcium sulfate anhydrite, calciumsulfate hemihydrate or calcium sulfate dihydrate, other hydrauliccomponents and combinations thereof. Mixtures of fly ashes are alsocontemplated for use. Silica fume (SKW Silicium Becancour, St. Laurent,Quebec, CA) is another preferred material.

While not wishing to be bound by theory, it is believed that the shapeof the fly ash particle contributes significantly to the characteristicsof this composition. The spherical shape of fly ash creates a “ballbearing” effect in the mix, improving workability of the compositionwithout increasing water requirements. In addition, some fly ashes havebeen shown to significantly decrease heat generation as the concretehardens and strengthens. Fly ash, as do all pozzolanic materials,generally provides increased strength gain for much longer periods thanmixes with Portland cement (St. Mary's Cement Inc., Detroit, Mich.)only. In the set product, there appears to be a larger proportion ofamorphous material than is found in gypsum or concrete, allowing moreflex in the material.

Another reason fly ash is preferred in this composition is the increasedlife cycle expectancy and increase in durability associated with itsuse. During the hydration process, fly ash chemically reacts with thecalcium hydroxide forming calcium silicate hydrate and calciumaluminate, which reduces the risk of leaching calcium hydroxide, makingthe composition less permeable. Fly ash also improves the permeabilityof hydraulic compositions by lowering the water-to-cement ratio, whichreduces the volume of capillary pores remaining in the set composition.The spherical shape of fly ash improves the consolidation of thecomposition, which also reduces permeability. It is also theorized thattricalcium aluminate, which is frequently present in fly ash, acts as aset accelerator to speed up the setting reactions.

In some embodiments of the invention, the hydraulic component includesat least 50% hydraulic fly ash by weight. Preferably, the hydrauliccomponent includes at least 55% hydraulic fly ash. More preferably, thehydraulic component includes at least 60% hydraulic fly ash. Morepreferably, the hydraulic component includes at least 65% hydraulic flyash. More preferably, the hydraulic component includes at least 70%hydraulic fly ash. More preferably, the hydraulic component includes atleast 75% hydraulic fly ash. More preferably, the hydraulic componentincludes at least 80% hydraulic fly ash. More preferably, the hydrauliccomponent includes at least 85% hydraulic fly ash. More preferably, thehydraulic component includes at least 90% hydraulic fly ash. Morepreferably, the hydraulic component includes at least 95% hydraulic flyash. More preferably, the hydraulic component includes at least 99%hydraulic fly ash. The remainder of the hydraulic component includes anyhydraulic materials or mixtures thereof. In another embodiment of thisinvention, the hydraulic component is essentially all fly ash.

The total composition preferably includes from about 25% to about 92.5%by weight of the hydraulic component. More preferably, the hydrauliccomponent makes up from about 40% to about 92.5% by weight of thecomposition. More preferably, the hydraulic component makes up fromabout 50% to about 92.5% by weight of the composition. More preferably,the hydraulic component makes up from about 55% to about 92.5% by weightof the composition. More preferably, the hydraulic component makes upfrom about 60% to about 92.5% by weight of the composition. Morepreferably, the hydraulic component makes up from about 65% to about92.5% by weight of the composition. More preferably, the hydrauliccomponent makes up from about 45% to about 85% by weight of thecomposition. More preferably, the hydraulic component makes up fromabout 50% to about 85% by weight of the composition. More preferably,the hydraulic component makes up from about 55% to about 85% by weightof the composition. More preferably, the hydraulic component makes upfrom about 60% to about 85% by weight of the composition. Morepreferably, the hydraulic component makes up from about 65% to about 85%by weight of the composition. More preferably, the hydraulic componentmakes up from about 40% to about 80% by weight of the composition. Morepreferably, the hydraulic component makes up from about 45% to about 80%by weight of the composition. More preferably, the hydraulic componentmakes up from about 50% to about 80% by weight of the composition. Morepreferably, the hydraulic component makes up from about 55% to about 80%by weight of the composition. More preferably, the hydraulic componentmakes up from about 60% to about 80% by weight of the composition. Morepreferably, the hydraulic component makes up from about 65% to about 80%by weight of the composition. More preferably, the hydraulic componentmakes up from about 40% to about 75% by weight of the composition. Morepreferably, the hydraulic component makes up from about 45% to about 75%by weight of the composition. More preferably, the hydraulic componentmakes up from about 50% to about 75% by weight of the composition. Morepreferably, the hydraulic component makes up from about 55% to about 75%by weight of the composition. More preferably, the hydraulic componentmakes up from about 60% to about 75% by weight of the composition. Morepreferably, the hydraulic component makes up from about 65% to about 75%by weight of the composition.

The polymer is a water-soluble, film-forming polymer, preferably a latexpolymer. The polymer can be used in either liquid form or as aredispersible powder. A particularly preferred latex polymer is a methylmethacrylate copolymer of acrylic acid and butyl acetate (Forton VF 774Polymer, EPS Inc. Marengo, Ill.).

Although the polymer is added in any useful amount, it is preferablyadded in amounts of from about 5% to 35% on a dry solids basis. Morepreferably, the composition includes from about 10% to about 35%polymer. More preferably, the composition includes from about 15% toabout 35% polymer. More preferably, the composition includes from about20% to about 35% polymer. More preferably, the composition includes fromabout 5% to about 30% polymer. More preferably, the composition includesfrom about 10% to about 30% polymer. More preferably, the compositionincludes from about 15% to about 30% polymer. More preferably, thecomposition includes from about 20% to about 30% polymer. Morepreferably, the composition includes from about 5% to about 25% polymer.More preferably, the composition includes from about 10% to about 25%polymer. More preferably, the composition includes from about 10% toabout 20% polymer. More preferably, the composition includes from about15% to about 20% polymer. More preferably, the composition includes fromabout 5% to about 15% polymer. More preferably, the composition includesfrom about 10% to about 15% polymer.

In order to form two interlocking matrix structures, water must bepresent to form this composition. The total water in the compositionshould be considered when adding water to the system. If the latexpolymer is supplied in the form of an aqueous suspension, water used todisperse the polymer should be included in the composition water. Anyamount of water can be used that produces a flowable mixture.Preferably, about 5 to about 35% water by weight is used in thecomposition. More preferably, the amount of water ranges from about 10%to about 35% by weight. More preferably, the amount of water ranges fromabout 15% to about 35% by weight. More preferably, the amount of waterranges from about 20% to about 35% by weight. More preferably, theamount of water ranges from about 25% to about 35% by weight. Morepreferably, the amount of water ranges from about 30% to about 35% byweight. More preferably, the amount of water ranges from about 15% toabout 30% by weight. More preferably, the amount of water ranges fromabout 10% to about 30% by weight. More preferably, the amount of waterranges from about 20% to about 30% by weight. More preferably, theamount of water ranges from about 25% to about 30% by weight. Morepreferably, the amount of water ranges from about 15% to about 25% byweight. More preferably, the amount of water ranges from about 10% toabout 25% by weight. More preferably, the amount of water ranges fromabout 20% to about 25% by weight. More preferably, the amount of waterranges from about 15% to about 20% by weight. More preferably, theamount of water ranges from about 10% to about 20% by weight of waterper 100 parts of dry hydraulic component.

The addition of water to the hydraulic component initiates hydrationreactions. Water of hydration is absorbed from the slurry to form thecrystalline matrix of the cementitious material. As the free waterdecreases, the polymer begins forming a film and hardens. Since both ofthese processes occur virtually simultaneously, the crystalline matrixof the cementitious material and the polymer film become intimatelyintertwined in each other, forming strong links between these twosubstances.

Any well-known additives for cements or polymer cements can be useful inany of the embodiments of the instant composition to modify it for aspecific purpose of application. Fillers are added for a variety ofreasons. The composition or finished product can be made even morelightweight if lightweight fillers, such as expanded perlite, otherexpanded materials or either glass, ceramic or plastic microspheres, areadded. Microspheres reduce the weight of the overall product byencapsulating gaseous materials into tiny bubbles that are incorporatedinto the composition thereby reducing its density. Foaming agents usedin conventional amounts are also useful for reducing the productdensity.

Conventional inorganic fillers and aggregates are also useful to reducecost and decrease shrinkage cracking. Typical fillers include sand,talc, mica, calcium carbonate, calcined clays, pumice, crushed orexpanded perlite, volcanic ash, rice husk ash, diatomaceous earth, slag,metakaolin, and other pozzolanic materials. Amounts of these materialsshould not exceed the point where properties such as strength areadversely affected. When very thin membranes or underlayments are beingprepared, the use of very small fillers, such as sand or microspheresare preferred.

Colorants are optionally added to change the color of the composition orfinished articles. Fly ash is typically gray in color, with the Class Cfly ash usually lighter than Class F fly ash. Any dyes or pigments thatare compatible with the composition may be used. Titanium dioxide isoptionally used as a whitener. A preferred colorant is Ajack Black fromSolution Dispersions, Cynthiana, Ky.

Set control additives that either accelerate or retard the setting timeof the hydraulic component are contemplated for use in thesecompositions. The exact additives will depend on the hydrauliccomponents being used and the degree to which the set time is beingmodified.

Reinforcing materials can be used to add strength to the composition.The additional of fibers or meshes optionally help hold the compositiontogether. Steel fibers, plastic fibers, such as polypropylene andpolyvinyl alcohols, and fiberglass are recommended, but the scope ofreinforcing materials is not limited hereby.

Superplasticizer additives are known to improve the fluidity of ahydraulic slurry. They disperse the molecules in solution so that theymove more easily relative to each other, thereby improving theflowability of the entire slurry. Polycarboxylates, sulfonated melaminesand sulfonated naphthalenes are known as superplasticizers. Preferredsuperplasticizers include ADVA Cast by Grace Construction Products,Cambridge, Mass. and Dilflo GW Superplasticizer of Geo SpecialtyChemicals, Cedartown, Ga. The addition of these materials allows theuser to tailor the fluidity of the slurry to the particular application.

Shrinkage reducing agents help decrease plastic shrinkage cracking asthe product dries. These generally function to modify the surfacetension so that the slurry flows together as it dries. Glycols arepreferred shrinkage reducing agents.

The hydraulic component, polymer, water and any optional components arecombined in a mixer and mixed until a homogeneous blend is obtained.Preferably, the mixer is a high shear mixer providing a short residencetime. For small batches of product, a typical laboratory blender is asuitable mixing device. For larger commercial operations, the use ofcommercially available continuous mixers manufactured by the PFT GMBHand Co. KG, based in Iphofen, Germany, are suitable. Continuous mixershave the capability of mixing as well as pumping the slurry in acontinuous manner to the point of application. These mixers have amixing chamber where all solid dry materials are blended together withthe liquid additives including water using a cage agitator rotating at ahigh speed. In the normal mode of operation, the blended cementitiousslurry continuously exits the mixing chamber and is pumped forward by aprogressive cavity pump (rotor-stator type pump) to the point ofapplication. The preferred PFT mixer models for this invention includePFT Mixing Pump G4, PFT Mixing Pump G5, PFT Monojet 2.13, PFT MixingPump T2E, PFT Mixing Pump MS1 and MS2.

Another preferred mixer is a high-shear batch mixer. The batch mixer ispreferred in some applications, particularly where the slurry must befed to more than one area of the manufacturing line. The wet ingredientsare changed to the mixer, followed by the dry components. After mixing,the entire batch is dumped into a pot for continuous distribution to theline. If distribution to more than one location is desired, multiplepumps with separate destinations can be used to distribute the slurryfrom the pot.

After mixing, the flowable slurry exits from the mixer and can be pouredinto a mold or extruder, onto release paper or onto a base mat forshaping into an appropriate shape. Any method may be used to shape thecomposition, including molding, extruding, troweling, calendaring,rolling, screeding, or any shaping method suitable for the article beingproduced.

The composition is also useful as a coating to give favorable propertiesto one or more sides of an article. A membrane for use as anunderlayment for ceramic tile can be prepared preferably by rolling orscreeding the slurry onto a base mat or scrim. The finished side of aceramic tile could be coated to provide a deformable surface. Statuaryor architectural moldings could be made of a different core, then coatedwith sufficient thickness of this composition to allow the piece to beshaped, carved, fit or detailed using common tools.

In the examples that follow, all components are measured by weightunless otherwise stated. The latex polymer used here, Forton VF774, wasin a liquid form and included 51% polymer solids and 49% water. In theexamples that follow, “water” refers to added water and does not includethat in the latex polymer. Of the amounts reported for the polymer, 51%of the amount is in the form of dry solids.

EXAMPLE 1

A slurry was made from the components from Mix 1 of Table 1. No water inaddition to that contained in the liquid polymer was added to form theslurry. TABLE 1 Components of Examples 1-4 Component Trade Name Mix 1Mix 2 Mix 3 Class C Fly Ash Bayou 66.8% 32.2% 0 Portland cement 0 32.2%62.4% Water 0 3.53 6.54 Acrylic Polymer Forton VF774 32.8% 31.58% 30.60%Latex Polycarboxylate Adva Cast 0.3% 0.3% 0.3% Superplasticizer ColorantAjack Black 8044 0.13%% 0.13% 0.13%

All of the above components were placed in a high-shear blender andblended for 30 seconds to form a slurry. A panel ¼″ (0.6 mm) inthickness and measuring 6″×12″ (15 cm×30 cm) was also cast in thelaboratory from the slurry. It was dried at room temperature for severalhours. As the panel dried, there was no shrinkage cracking of thematerial. The nature of the composite was similar to that of rubber,only it was harder and more flexible.

The flexibility of the resulting panel is demonstrated in FIG. 1. Thepanel was flexed along its 12″ (30 cm) length until an archapproximately 4″ (10 cm) in height was formed. There was no visiblecracking as a result of flexing the material. Even after such largedeformations, the panel regained its original shape with no signs ofdamage.

Fatigue of the material was tested by repeated flexing of the cast flatpanel into a 4″ (10 cm) arch as shown in FIG. 1. After 50 such flexings,there was no sign of cracking or damage. The material has an ultimatetensile strain capacity of >2% and a tensile toughness of 30 inch-poundsper square inch (435 N-m/m²).

The flow behavior of the slurry was characterized by filling acalibrated brass cylinder 4″ (10.2 cm) in height and 2″ (5.1 cm) ininternal diameter with the slurry. The cylinder was lifted up, allowingthe slurry to exit from the bottom of the cylinder and spread. An 11″(28 cm), self-leveled patty formed from the slurry, as shown in FIG. 2.

EXAMPLE 2

A slurry from each of Mix 2 and Mix 3 in Table 1 was prepared accordingto the method of Example 1. Circular patties were cast from each of theslurries as described in Example 1 and allowed to dry. The patty fromMix 2 is shown in FIG. 3, while FIG. 4 shows the patty of Mix 3. Mixes 2and 3 developed significant shrinkage cracking as the patty dried, mostof it within the first two hours after casting. The fly ash compositionof Example 1 developed no cracking at all as shown in FIG. 2. Thisdemonstrates the superior shrinkage cracking resistance and dimensionalstability of compositions that include more than 50% fly ash.

EXAMPLE 3

Tensile properties of a sample of Mix 1 were tested in a Model 810close-loop, displacement-controlled testing machine by MTS Systems Corp.of Eden Prairie, Minn. A rectangular specimen was prepared measuring 8″in length, 2″ wide and ¼″ in thickness. Notches ½″ long were cut on bothsides of the specimen at mid height. Testing was conducted when thespecimen was 28 days of age. Results of the tests are shown in Table IIbelow. TABLE II Physical Properties of Mix 1 Plain Property Mix 1Concrete Ultimate Tensile Strain (%)  2.00 0.01 Tensile Toughness^(a),lb-inch/inch² 32.0 0.12 (g-cm/cm²) (5,690)    (21)   Tensile Strength,psi 246  290    (kg/cm²) (17.2) (20.3)  Modulus of Elasticity, psi 279 20000    (kg/cm²) (19.5) (1400)  

Results for concrete are those reported in the literature. “Plainconcrete” is the set product of Portland cement, sand, aggregate andwater. This test shows that the fly ash composition has exceptionalductility and toughness as indicated by the ultimate tensile strain andtensile toughness numbers. Tensile toughness represents energy requiredto fracture a specimen per unit cross-sectional area. In both of thesetests, the fly ash composition of Mix 1 showed tensile strain andtensile toughness about 200 times greater than concrete. Increasedelasticity, approaching that of rubber, is measured by the severedecrease in the modulus of elasticity over concrete.

EXAMPLE 4

The use of other pozzolanic materials was tested by replacing a portionof the fly ash with other pozzolans. Three compositions were made usingsilica fume, as shown in Table III below. TABLE III Components ofExample 4 Ingredient Mix 4 Mix 5 Mix 6 Class C Fly Ash (Bayshore, MI)58.06 59.37 62.91 Silica Fume 6.45 3.13 3.31 Water 3.21 6.86 0.65Acrylic Polymer Latex (Forton VF77) 31.63 30.64 32.47 Polymer solidscontent - 51% and Water content - 49% Polycarboxylate superplasticizer0.65 0.00 0.66 (Adva Cast) Colorant (Ajack Black AJ 61) 0.00 0.00 0.00

The mixes in Table III above were mixed and subjected to the patty testdescribed in Example 1. In Mix 4, 10% of the fly ash was replaced withsilica fume. Mixes 5 and 6 replaced only 5% of the fly ash with silicafume. A superplasticizer was added to Mixes 4 and 6, but not to Mix 5.

Patties cast using Mix 4, Mix 5 and Mix 6 are shown in FIGS. 5, 6 and 7,respectively. All patties were self-leveling and produced no stresscracks.

While particular embodiments of the present fly ash composition andmethod for making it has been shown and described, it will beappreciated by those skilled in the art that changes and modificationsmay be made thereto without departing from the invention in its broaderaspects and as set forth in the following claims.

1. A composition for the manufacture of articles comprising: a hydrauliccomponent comprising at least 50% fly ash; a water-soluble, film-formingpolymer; and water.
 2. The composition of claim 1 wherein said hydrauliccomponent consists essentially of fly ash.
 3. The composition of claim 1wherein said fly ash comprises Class C fly ash.
 4. The composition ofclaim 1 wherein the composition comprises at least 25% of said hydrauliccomponent by weight.
 5. The composition of claim 4 wherein thecomposition comprises at least 40% of said hydraulic component by weight6. The composition of claim 1 wherein said polymer comprises at least 5%by weight of the composition.
 7. The composition of claim 1 wherein saidcomposition further comprises one or more of the group consisting ofdispersants, surfactants, water reducing agents, set accelerators, setretarders, foaming agents, defoamers, colorants, shrinkage reducingagents, reinforcing fibers and fillers.
 8. The composition of claim 7wherein said fillers comprise inorganic minerals, lightweight fillers,organic fillers and aggregates.
 9. An article comprising a set mixtureof a water-soluble, film-forming polymer and a hydraulic componentcomprising at least 50% fly ash.
 10. An article of manufacturecomprising a set mixture a water-soluble, film-forming polymer and ahydraulic component comprising at least 50% fly ash.
 11. The article ofclaim 10 wherein said hydraulic component consists essentially of flyash.
 12. The article of claim 10 wherein said fly ash comprises highlime fly ash or class C fly ash per ASTM C-618.
 13. The article of claim10 wherein said article comprises at least one of a mortar, a grout, apanel, statuary, a cast article, an injection molded article and ashaped article.
 14. An article of manufacture comprising a continuousphase of a set hydraulic component comprising at least 50% fly ash and adiscontinuous polymer film.
 15. The article of claim 14 wherein saidhydraulic component consists essentially of fly ash.
 16. The article ofclaim 14 wherein said article is deformable.
 17. The article of claim 14wherein said article comprises at least one of a mortar, a grout, apanel, statuary, a cast article, an injection molded article and ashaped article.
 18. A method of making flexible articles comprising:making a slurry of a hydraulic component comprising at least 50% flyash, a water-soluble, film-forming polymer and water; forming thearticle; and allowing the slurry to set.
 19. The method of claim 18wherein said making step comprises mixing a homogonous slurry.
 20. Themethod of claim 18 wherein said making step comprises mixing thecomponents in a high-shear mixer.
 21. The method of claim 18 whereinsaid forming step comprises at least one of pouring, casting, cutting,carving, rolling, troweling, screeding, molding and shaping the article.22. The method of claim 18 wherein said allowing step comprises dryingsaid article in an oven.